(ethene)[N,N,N-tris(2-pyridylmethyl-κN)amine-κN]rhodium(I) hexafluorophosphate | 198962-37-7

• 英文名称: (ethene)[N,N,N-tris(2-pyridylmethyl-κN)amine-κN]rhodium(I) hexafluorophosphate
• CAS: 198962-37-7
• 化学式: C₂₀H₂₂N₄Rh*F₆P
• 分子量: 566.291
• InChiKey: VJJLVRMBSIVELW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  (ethene)[N,N,N-tris(2-pyridylmethyl-κN)amine-κN]rhodium(I) hexafluorophosphate 在 air 作用下， 以 neat (no solvent) 为溶剂， 生成 (2-peroxyethyl-κ2C1,O2)[N,N,N-tris(2-pyridylmethyl-κN)amine-κN]rhodium(III) hexafluorophosphate
  参考文献：
  名称：

  3‐Metalla‐1,2‐dioxolanes and Their Reactivity

  摘要：

  AbstractThe ethene complexes [MI(CH2CH2)]+ (M = Ir, Rh) can be oxygenated by molecular oxygen or air in the solid state, to form isolable unsubstituted 3‐metalla‐1,2‐dioxolanes [MIII(CH2CH2OO‐κ2C1,O2)]+. Such selectivity could not be achieved in solution. The stereoselectivity of the oxygenation process is highly dependent on the ligand, the metal and the counterion used. Oxygenation of [(tpa)M(CH2CH2)]PF6 {tpa = tri(2‐pyridylmethyl)amine; 4PF6, 7PF6} results in the formation of two isomeric 3‐metalladioxolanes, whereas oxygenation of [(tpa)M(CH2CH2)]BPh4 (4BPh4, 7BPh4) only yields one isomer. Furthermore, oxygenation of [(Metpa)Rh(CH2CH2)]PF6 {14PF6, Metpa = [(6‐methyl‐2‐pyridyl)methyl]bis(2‐pyridylmethyl)amine} proved to be much slower than that of [(tpa)Rh(CH2CH2)]PF6 (7PF6). The solid propene complex [(tpa)Rh(CH2CHCH3)]BPh4 (23BPh4) loses propene on reaction with molecular oxygen, and selectively forms the peroxo complex [(tpa)Rh(η2‐O2)]BPh4 (24BPh4). The obtained 3‐metalla‐1,2‐dioxolanes rearrange, both in the solid state and in solution, to formylmethyl hydroxy complexes on exposure to photons or protons. The isomeric 3‐rhoda‐1,2‐dioxolanes [(tpa)Rh(CH2CH2OO‐κ2C1,O2)]+ 8a+ and 8b+ differ in reactivity. On exposure of a solution of 8aPF6/8bPF6 to glass‐filtered daylight, isomer 8b+ rearranges to form the formylmethyl hydroxy complex 9b+. This rearrangement is three times faster than the rearrangement of 8a+ to 9a+. The iridadioxolanes are much more reactive than the corresponding rhodadioxolanes, whereas the iridium formylmethyl hydroxy complexes are less reactive than the corresponding rhodium formylmethyl hydroxy complexes. The tpa formylmethyl hydroxy complexes react reversibly with carbon dioxide to form formylmethyl hydrogen carbonate complexes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

  DOI：

  10.1002/ejic.200390139
• 作为产物：
  描述：

  ethene(3,1-dimethyl-3,11,17,18-tetraazatricyclo[11.3.1.1(5,9)]octadeca-1(17),5(18),6,8,13,15-hexaene-κ4N1,N2,N3,N4)rhodium(I) hexafluorophosphate 在 air 作用下， 以 neat (no solvent) 为溶剂， 生成 (ethene)[N,N,N-tris(2-pyridylmethyl-κN)amine-κN]rhodium(I) hexafluorophosphate 、 (formylmethyl-κC1)(hydroxy)(3,1-dimethyl-3,11,17,18-tetraazatricyclo[11.3.1.1(5,9)]octadeca-1(17),5(18),6,8,13,15-hexaene-κ4N1,N2,N3,N4)rhodium(III) hexafluorophosphate
  参考文献：
  名称：

  3‐Metalla‐1,2‐dioxolanes and Their Reactivity

  摘要：

  AbstractThe ethene complexes [MI(CH2CH2)]+ (M = Ir, Rh) can be oxygenated by molecular oxygen or air in the solid state, to form isolable unsubstituted 3‐metalla‐1,2‐dioxolanes [MIII(CH2CH2OO‐κ2C1,O2)]+. Such selectivity could not be achieved in solution. The stereoselectivity of the oxygenation process is highly dependent on the ligand, the metal and the counterion used. Oxygenation of [(tpa)M(CH2CH2)]PF6 {tpa = tri(2‐pyridylmethyl)amine; 4PF6, 7PF6} results in the formation of two isomeric 3‐metalladioxolanes, whereas oxygenation of [(tpa)M(CH2CH2)]BPh4 (4BPh4, 7BPh4) only yields one isomer. Furthermore, oxygenation of [(Metpa)Rh(CH2CH2)]PF6 {14PF6, Metpa = [(6‐methyl‐2‐pyridyl)methyl]bis(2‐pyridylmethyl)amine} proved to be much slower than that of [(tpa)Rh(CH2CH2)]PF6 (7PF6). The solid propene complex [(tpa)Rh(CH2CHCH3)]BPh4 (23BPh4) loses propene on reaction with molecular oxygen, and selectively forms the peroxo complex [(tpa)Rh(η2‐O2)]BPh4 (24BPh4). The obtained 3‐metalla‐1,2‐dioxolanes rearrange, both in the solid state and in solution, to formylmethyl hydroxy complexes on exposure to photons or protons. The isomeric 3‐rhoda‐1,2‐dioxolanes [(tpa)Rh(CH2CH2OO‐κ2C1,O2)]+ 8a+ and 8b+ differ in reactivity. On exposure of a solution of 8aPF6/8bPF6 to glass‐filtered daylight, isomer 8b+ rearranges to form the formylmethyl hydroxy complex 9b+. This rearrangement is three times faster than the rearrangement of 8a+ to 9a+. The iridadioxolanes are much more reactive than the corresponding rhodadioxolanes, whereas the iridium formylmethyl hydroxy complexes are less reactive than the corresponding rhodium formylmethyl hydroxy complexes. The tpa formylmethyl hydroxy complexes react reversibly with carbon dioxide to form formylmethyl hydrogen carbonate complexes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

  DOI：

  10.1002/ejic.200390139

文献信息

• 3-Rhoda-1,2-dioxolanes through Dioxygenation of a Rhodium-Ethene Complex by Air
  作者：Monique Krom、Ruud G. E. Coumans、Jan M. M. Smits、Anton W. Gal

  DOI：10.1002/1521-3773(20010601)40:11<2106::aid-anie2106>3.0.co;2-o

  日期：2001.6.1

  Proposed as intermediates in the catalytic oxidation of olefins to ketones, 3-rhoda-1,2-dioxolanes (κ2 C1 ,O2 -2-peroxyethyl rhodium complexes) have now been prepared by oxygenation of solid [(N4 -ligand)RhI (ethene)]PF6 with air. This process leads to stable isomeric 3-rhoda-1,2-dioxolanes A and B. Upon substitution of PF6- by BPh4- only isomer B is obtained. The X-ray structure of isomer B is presented.
• Oxidation of RhI(olefin) Fragments to 2-Rhoda(III)oxetanes
  作者：Bas de Bruin、Mark J. Boerakker、Jack J. J. M. Donners、Boukje E. C. Christiaans、Paul P. J. Schlebos、René de Gelder、Jan M. M. Smits、Anthony L. Spek、Anton W. Gal

  DOI：10.1002/anie.199720641

  日期：1997.10.17